CN104471119A - Method of producing fine amorphous polymer fibres, fine amorphous polymer|fibres, and spinneret for producing such fibres - Google Patents

Method of producing fine amorphous polymer fibres, fine amorphous polymer|fibres, and spinneret for producing such fibres Download PDF

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Publication number
CN104471119A
CN104471119A CN201380037820.1A CN201380037820A CN104471119A CN 104471119 A CN104471119 A CN 104471119A CN 201380037820 A CN201380037820 A CN 201380037820A CN 104471119 A CN104471119 A CN 104471119A
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fiber
spinning
melt
amorphous
pei
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CN201380037820.1A
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CN104471119B (en
Inventor
理查德·彼得斯
戴维·沃伦
迈克尔·林赛
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SABIC Global Technologies BV
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SABIC Innovative Plastics IP BV
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D4/00—Spinnerette packs; Cleaning thereof
    • D01D4/02—Spinnerettes
    • D01D4/025—Melt-blowing or solution-blowing dies
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/06—Feeding liquid to the spinning head
    • D01D1/09—Control of pressure, temperature or feeding rate
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D4/00—Spinnerette packs; Cleaning thereof
    • D01D4/06—Distributing spinning solution or melt to spinning nozzles
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/084—Heating filaments, threads or the like, leaving the spinnerettes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/098—Melt spinning methods with simultaneous stretching
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/14—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/298—Physical dimension

Abstract

A method, including extruding a melt including an amorphous polymer composition through a spinneret under a pressure from 400 to 1500 psi to produce a spun fiber; collecting the spun fiber on a feeding roll without drawing the spun fiber; producing a solidified fiber from the spun fiber. The solidified fiber can have a dpf of from greater than 0 to 2.5 dpf, and a shrinkage less than or equal to 2%. The method can also include collecting the solidified fiber onto a spool without subjecting the solidified fiber to a drawing step. A spinneret for producing fibers of at most 2.5 dpf from a composition comprises an amorphous polyetherimide, the spinneret comprising a die having a plurality of round melt channels but no distribution plates. Fibers produced by the method and from the spinneret are also disclosed.

Description

Produce the method for meticulous amorphous polymer fiber, meticulous amorphous polymer fiber and the spinning head for the production of this fiber
Technical field
Present invention relates in general to fiber and system, method and apparatus for the production of fiber.More specifically, the present invention relates to meticulous DENIER amorphous polymer fiber (the DENIER polyether-imide fiber as meticulous), and when not extracting spinning fibre out, by system, the method and apparatus of melt spinning polymer for the production of such fiber.
Background technology
Use for the melt of merocrystalline material and physical characteristic, namely low melt viscosity, excellent heat endurance and crystallinity have optimized the method set up completely and synthetic fiber a lot of year produced by process equipment.Traditionally, used merocrystalline manufacture of materials synthetic fiber, these merocrystalline materials have very low viscosity in the molten state, and need processing method or die design method to produce uniform melt distribution on spinneret hole pattern.Design spinning head (spinneret) is to contribute to being uniformly distributed of melt.But these designs advantageously do not use amorphous polymer, comprise thermoplastic such as PEI.Use melt spinning method that amorphous thermoplastics processing is become fiber, be the new method of attempting on traditional molten spinning silk thread, there is limited success.The design that some in these problems can be attributed to process equipment is not suitable for amorphous material.Although need, or not for when not extracting the fiber of synthesis out, by amorphous thermoplastic being produced into by its melt spinning fine fiber to reduce custom-designed molten spinning silk thread (melt spinning line) or the spinning head of their DENIER.
Traditionally, used merocrystalline manufacture of materials synthetic fiber, these merocrystalline materials are extracting post crystallization out from spinning head, and melt spinning becomes every fine rule 2 DENIER (dpf) and following meticulous denier fiber easily.Amorphous material does not form crystal after extraction, and therefore using conventional melt spinning method, the extraction section of described process is stretched to 2dpf and following period, does not have sufficient percentage elongation and intensity.Traditional processing scheme is not suitable for some amorphous engineered thermoplastic composition (as PEI (PEI) spherolite) to be converted to meticulous denier fiber, because traditional method causes the restriction for realizing how meticulous fiber.There is demand in the polyether-imide fiber for the dpf with 2 or lower.Need development approach and process technology, it will allow by amorphous engineering thermoplasties as PEI produces 2dpf and lower fiber.Current trial conventional method carries out the production of meticulous denier fiber, and is extend in operation in rear transfer process to extract out, maybe can not extract out and be low to moderate 2dpf and lower.
Summary of the invention
A kind of embodiment relates to a kind of method, to comprise the steps: under the pressure of 400 to 1500psi by spinning head extruded polymer melt to produce spinning fibre, in propelling roller (forwardingroll), sometimes also referred to as on feed roller, collect spinning fibre, the fiber of solidification is produced by spinning fibre, and when not making the fiber experience of solidification extract step out, by the fiber collecting of solidification on bobbin (spool).Melt can comprise amorphous polymer composition, as PEI.The fiber of solidification can have the dpf be greater than in 0 to 2.5dpf scope, and is less than or equal to the shrinkage factor of 2%.
Other embodiment relate to have be less than 2.5 DENIER and be greater than 0 to the unpumped amorphous polymer fiber of shrinkage factor being less than or equal to 2%.
Other embodiment is still had to relate to the spinning head of the unpumped polyether-imide fiber of amorphous for being produced (comprising amorphous PEI, as PEI) 2.5dpf at the most by composition.This spinning head can avoid the use of distribution grid, and can than comprise distribution grid spinning head operating pressure low at least 40% pressure under operate.This spinning head can comprise the screen modules filter (screen pack filter) that is combined with die head so that composition is distributed to die head.This die head can have multiple circular melt canal, and wherein, each circular melt canal has length and diameter, and wherein, the length of each circular melt canal: the ratio of diameter is 2:1 to 6:1.
Accompanying drawing explanation
With reference to following description and the claim of enclosing, and accompanying drawing will understand these and other feature, aspect and advantage better, wherein:
Fig. 1 is the schematic diagram of the prior art nozzle design of non-existent two kinds of distribution grids in the design being included in various embodiment of the present invention;
Fig. 2 is according to various embodiment of the present invention, has the schematic diagram of 72 hole nozzle design of the central core distribution of three concentric rings of charging capillary;
Fig. 3 is according to various embodiment of the present invention, has the schematic diagram of 144 hole nozzle design of screen modules filter for distributing of six concentric rings of charging capillary;
Fig. 4 is the schematic diagram of prior art fiber production method, can be revised with the spinning head adopted according to various embodiment of the present invention.
Should be understood that, various embodiment is not limited to the layout and means that show in the accompanying drawings.
Detailed description of the invention
In following detailed description and the claim of enclosing, will mention many terms, they are defined as has following implication:
" DENIER " is the measurement unit of the linear mass density for fiber.In the application and claim, be defined as every 9000 meters by gram quality.
As used in the application and claim, " spinning head " is multi-orifice devices, by its extrusion plastic polymer melt to form fiber.
Whether no matter show clearly, numerical value all in this article all supposes to be modified by term " about ".Term " about " typically refers to those skilled in the art and is thought the quantitative range (such as, having same function or result) being equal to described value.In many cases, term " about " can comprise the quantity being rounding to nearest significant digits.
Embodiments of the present invention relate to the method for being produced meticulous denier fiber by engineering thermoplasties's (as PEI).
Formed in the conventional process of fiber by melt extrusion, high pressure (1000 to 2000psi) crosses being uniformly distributed of the melt of spinneret hole for maintenance, and wherein adopt chilling apparatus with controlled cooling model speed, and therefore when it is extracted out from spinning head the degree of crystallinity of material be critical.Various embodiment of the present invention avoids these conditions, and they are not desirable for amorphous engineering thermoplasties is processed into meticulous denier fiber.According to the embodiment of the present invention, pressure (400 to 2000psi) can be reduced to reduce the shearing under melt state on material, and therefore reduce the negative effect of that drawback, i.e. the drippage of fibre bundle (fiber strand) or fragmentation.Have been found that the higher viscosity of amorphous thermoplastic in melt state, enough back pressures can be provided in systems in which to be uniformly distributed melt to cross spinning head.After leaving spinning head, not coolant in quenching cabinet (quench cabinet), and in fact, unexpectedly have benefited from this space, use heat with the cooling rate of the amorphous material that slows down, and reduce being spun into the quenching impact that material causes.Use above-described method, can be successfully used to polyether-imide fiber to be melt-spun into 2dpf and lower according to method of the present invention.
A kind of embodiment relates to the method comprising series of steps.These steps can be continuous print or discrete.The method can comprise by spinning head melt extrusion to produce the step of spinning fibre.
Under pressure in the scope with lower limit and/or the upper limit, spinning head melt extrusion can be passed through.This scope can comprise or not comprise lower limit and/or the upper limit.Lower limit and/or the upper limit can be selected from 100,150,200,250,300,350,400,450,500,550,600,650,700,750,800,850,900,950,1000,1050,1100,1150,1200,1250,1300,1350,1400,1450,1500,1550,1600,1650,1700,1750,1800,1850,1900,1950 and 2000psi.Such as, according to some preferred embodiment, spinning head melt extrusion can be passed through under the pressure of 400 to 1500psi.
Melt can comprise amorphous polymer composition.Amorphous polymer composition can have the melt flow in the scope with lower limit and/or the upper limit.This scope can comprise or not comprise lower limit and/or the upper limit.Lower limit and/or the upper limit can be selected from 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43,44,45,46,47,48,49,50,51,52,53,54,55,56,57,58,59 and 60g/10min in any one.Such as, according to some preferred embodiment, amorphous polymer composition can have the melt flow of every 10min 4 to 18 grams (g/10min).
Melt can comprise one or more crystalline material.Amorphous polymer composition can comprise polyimides.Polyimides comprises PEI and polyether imide copolymer.PEI can be selected from (i) polyetherimide homopolymer, such as, PEI, (ii) polyether imide copolymer, such as, polyetherimide sulfone, and (iii) their combination.PEI is known polymer, and sold by SABIC Innovative Plastics with under SILTEM* trade mark (SABICInnovative Plastics IP B.V. trade mark).
In one embodiment, PEI has formula (1):
Wherein, a is greater than 1, such as, 10 to 1,000 or more, or more specifically, 10 to 500.
Group V in formula (1) is the tetravalent linker of the combination (" polyetherimide sulfone ") comprising ether group (as used in this article " PEI ") or ether group and arlydene sulfuryl group.Such connector including but not limited to: (a) has group that the is replacement of 5 to 50 carbon atoms or unsubstituted, saturated, undersaturated or aromatic monocyclic and many rings, alternatively with ether group, arlydene sulfuryl group or ether group and arlydene sulfuryl group combination replace; B () has the replacement of 1 to 30 carbon atom or unsubstituted, linear or branch, saturated or unsaturated alkyl group and replaces with the combination that ether group or ether group, arlydene sulfuryl group and arlydene sulfuryl are rolled into a ball alternatively; Or comprise the combination of above-mentioned at least one.The other replacement be applicable to comprises, but is not limited to, ether, acid amides, ester and comprise the combination of above-mentioned at least one.
R group in formula (1) including but not limited to substituted or unsubstituted divalent organic group, as: (a) has aromatic hydrocarbon group and their halide derivative of 6 to 20 carbon atoms; B () has the straight or branched alkylidene group of 2 to 20 carbon atoms; C () has the cycloalkylidene group of 3 to 20 carbon atoms, or the divalent group of (d) formula (2):
Wherein, Q 1including but not limited to divalent moiety, as-O-,-S-,-C (O)-,-SO 2-,-SO-,-C yh 2y-(y is the integer of 1 to 5), and their halide derivative, comprise perfluoroalkylene group.
In one embodiment, connector V is including but not limited to the tetravalence aromatic group of formula (3):
Wherein, W is divalent moiety, comprises-O-,-SO 2-, or the group of formula-O-Z-O-, wherein, two valence links of-O-or-O-Z-O-group are 3,3 ', 3,4 ', 4,3 ', or 4,4 ' position, and wherein, Z comprises, but be not limited to, the divalent group of formula (4):
Wherein, Q comprises, but is not limited to divalent moiety, comprises-O-,-S-,-C (O) ,-SO 2-,-SO-,-C yh 2y-(y is the integer of 1 to 5), and their halide derivative, comprise perfluoroalkylene group.
In a kind of concrete embodiment, PEI comprises and is greater than 1, particularly, and 10 to 1000, or more specifically, the construction unit of 10 to 500 formulas (5):
Wherein, T is the group of-O-or formula-O-Z-O-, and wherein, two valence links of-O-or-O-Z-O-group are 3,3 ', 3,4 ', 4,3 ', or 4,4 ' position; Just as defined above, Z is the divalent group of formula (3); And just as defined above, R is the divalent group of formula (2).
In the embodiment that another kind is concrete, polyetherimide sulfone is the PEI comprising ether group and sulfuryl group, and wherein, in formula (1), at least the connector V of 50mol% and radicals R comprise the arlydene sulfuryl group of divalence.Such as, all connector V, but there is no radicals R, arlydene sulfuryl group can be comprised; Or all radicals R, but do not have connector V can comprise arlydene sulfuryl group; Or if the total mole of part of the V and R group that comprise aryl sulfone group is more than or equal to 50mole%, arlydene sulfone can exist with the some parts of connector V and R group.
Even more specifically, polyetherimide sulfone can comprise and be greater than 1, particularly, and 10 to 1000, or more specifically, the construction unit of 10 to 500 formulas (6):
Wherein, Y is-O-,-SO 2-, or the group of formula-O-Z-O-, wherein ,-O-, SO 2-, or two valence links of-O-Z-O-group are 3,3 ', 3,4 ', 4,3 ', or 4,4 ' position, wherein, Z is the divalent group of the formula (3) as limited above, and if comprise-SO at the 50mole% that is greater than of the summation of the middle Y molal quantity+R molal quantity of formula (2) 2-group, R is the divalent group of the formula (2) as limited above.
Should be understood that, PEI and polyetherimide sulfone can comprise the connector V of ether or ether and sulfuryl group alternatively, the such as connector of formula (7):
Comprise the acid imide unit of such connector usually with 0 to 10mol%, particularly, the amount of the unit sum of 0 to 5mol% exists.In one embodiment, other connector V is not had to be present in PEI and polyetherimide sulfone.
In the embodiment that another kind is concrete, PEI comprises the construction unit of 10 to 500 formulas (5), and polyetherimide sulfone comprises the construction unit of 10 to 500 formulas (6).
PEI and polyetherimide sulfone can be prepared by any applicable method.In one embodiment, PEI and polyether imide copolymer comprise polycondensation polymerization (polycondensation polymerization process) and halogen displacement polymerization (halo-displacement polymerization process).
Polycondensation method can comprise the method for the preparation of the PEI with structure (1), is referred to as nitration method (nitro-displacement process) (in formula (8), X is nitro).In a kind of example of nitration method, with 99% nitric acid nitrating N-Methyl-o-phthalimide to produce the mixture of N-methyl-4-nitrophthalimide (4-NPI) and N-methyl-3-nitro phthalimide (3-NPI).After purification, when there is phase transfer catalyst, the mixture comprising the 3-NPI of about 95 parts 4-NPI and 5 part reacts with the disodium salt of bisphenol-A (BPA) in toluene.This reaction produces BPA-double imide and NaNO being called in nitration step 2.After purification, BPA-double imide and phthalic anhydride in acid imide exchange reaction, to provide BPA dianhydride (BPADA), itself so react to provide product polyether acid imide with diamines (e.g., being in the m-phenylenediamine (MPD) in o-dichlorohenzene in sub-amidatioon-polymerization procedure).
Other diamines is also possible.The example of the diamines be applicable to comprises: m-phenylene diamine (MPD); P-phenylenediamine (PPD); 2,4-diaminotoluene; 2,6-diaminotoluene; MXDP; Terephthaldehyde's base diamines; Benzidine; 3,3 '-dimethylbenzidine; 3,3 '-dimethoxy benzidine; 1,5-diaminonaphthalene; Two (4-aminophenyl) methane; Two (4-aminophenyl) propane; Two (4-aminophenyl) thioether; Two (4-aminophenyl) sulfone; Two (4-aminophenyl) ether; 4,4 '-diamino-diphenyl propane; 4,4 '-aminodiphenylmethane (4,4 '-methylene dianiline (MDA)); 4,4 '-diamino diphenyl sulfide; 4,4 '-diamino diphenyl sulfone; 4,4 '-diamino-diphenyl ether (4,4 '-oxygen dianil); 1,5-diaminonaphthalene; 3,3 '-dimethylbenzidine; 3-methyl heptamethylene diamines; 4,4-dimethyl heptamethylene diamines; 2,2 ', 3,3 '-tetrahydrochysene-3,3,3 ', 3 '-tetramethyl-1,1 '-spiral shell two [1H-indenes]-6,6 '-diamines; 3,3 ', 4,4 '-tetrahydrochysene-4,4,4 ', 4 '-tetramethyl-2,2 '-spiral shell two [2H-1-benzo-pyrans]-7,7 '-diamines; 1,1 '-bis-[1-amino-2-methyl-4-phenyl] cyclohexane, and their isomers and comprise mixture and the blend of above-mentioned at least one.In one embodiment, diamines is specific aromatic diamine, especially, and m-phenylene diamine (MPD) and p-phenylenediamine (PPD), and the mixture comprising above-mentioned at least one.
The dianhydride be applicable to that can use together with diamines, comprises and is not limited to two [4-(3, the 4-di carboxyl phenyloxy) phenyl] propane dianhydride of 2,2-; 4,4 '-bis-(3,4-di carboxyl phenyloxy) diphenyl ether dianhydride; 4,4 '-bis-(3,4-di carboxyl phenyloxy) diphenylsulfide dianhydride; 4,4 '-bis-(3,4-di carboxyl phenyloxy) benzophenone dianhydride; 4,4 '-bis-(3,4-di carboxyl phenyloxy) diphenyl sulfone dianhydride; Two [4-(2, the 3-di carboxyl phenyloxy) phenyl] propane dianhydride of 2,2-; 4,4 '-bis-(2,3-di carboxyl phenyloxy) diphenyl ether dianhydride; 4,4 '-bis-(2,3-di carboxyl phenyloxy) diphenylsulfide dianhydride; 4,4 '-bis-(2,3-di carboxyl phenyloxy) benzophenone dianhydride; 4,4 '-bis-(2,3-di carboxyl phenyloxy) diphenyl sulfone dianhydride; 4-(2,3-di carboxyl phenyloxy)-4 '-(3,4-di carboxyl phenyloxy) diphenyl-2,2-propane dianhydride; 4-(2,3-di carboxyl phenyloxy)-4 '-(3,4-di carboxyl phenyloxy) diphenyl ether dianhydride; 4-(2,3-di carboxyl phenyloxy)-4 '-(3,4-di carboxyl phenyloxy) diphenylsulfide dianhydride; 4-(2,3-di carboxyl phenyloxy)-4 '-(3,4-di carboxyl phenyloxy) benzophenone dianhydride; 4-(2,3-di carboxyl phenyloxy)-4 '-(3,4-di carboxyl phenyloxy) diphenyl sulfone dianhydride; Two (2, the 3-di carboxyl phenyloxy) benzene dianhydride of 1,3-; Isosorbide-5-Nitrae-bis-(2,3-di carboxyl phenyloxy) benzene dianhydride; Two (3, the 4-di carboxyl phenyloxy) benzene dianhydride of 1,3-; Isosorbide-5-Nitrae-bis-(3,4-di carboxyl phenyloxy) benzene dianhydride; 3,3 ', 4,4 '-biphenyltetracaboxylic dianhydride; 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride; Naphthalenedicarboxylic acid dianhydride, as 2,3,6,7-naphthalenedicarboxylic acid dianhydride, etc.; 3,3 ', 4,4 '-diphenyl sulfonic acid tetracarboxylic dianhydride; 3,3 ', 4,4 '-diphenyl ether tetracarboxylic dianhydride; 3,3 ', 4,4 '-dimethyl diphenyl silane tetracarboxylic dianhydride; 4,4 '-bis-(3,4 di carboxyl phenyloxy) diphenylsulfide dianhydride; 4,4 '-bis-(3,4-di carboxyl phenyloxy) diphenyl sulfone dianhydride; 4,4 '-bis-(3,4-di carboxyl phenyloxy) diphenyl propane dianhydride; 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride; Two (phthalic acid) phenyl sulfonium compound oxide dianhydride (bis (phthalic) phenylsulphineoxide dianhydride); To phenylene-bis-(triphenyl phthalic acid) dianhydride; Metaphenylene-bis-(triphenyl phthalic acid) dianhydride; Two (triphenyl phthalic acid)-4,4 '-diphenyl ether dianhydride; Two (triphenyl phthalic acid)-4,4 '-diphenyl methane dianhydride; 2,2 '-bis-(3,4-dicarboxyphenyi) hexafluoropropane dianhydride; 4,4 '-oxydiphthalic acid dianhydride; Pyromellitic acid anhydride; 3,3 ', 4,4 '-diphenylsulfone acid dianhydride; 4,4 '-bisphenol A dianhydride; Quinhydrones two O-phthalic acid dianhydride; 6,6 '-bis-(3,4-di carboxyl phenyloxy)-2,2 ', 3,3 '-tetrahydrochysene-3,3 ', 3,3 '-tetramethyl--1,1 '-spiral shell two [1H-indenes] dianhydride; 7,7 '-bis-(3,4-di carboxyl phenyloxy)-3,3 ', 4,4 '-tetrahydrochysene-4,4,4 ', 4 '-tetramethyl--2,2 '-spiral shell two [2H-1-chromene] dianhydride; 1,1 '-bis-[1-(3,4-di carboxyl phenyloxy)-2-methyl 4-phenyl] cyclohexane dianhydride; 3,3 ', 4,4 '-diphenylsulfone acid dianhydride; 3,3 ', 4,4 '-diphenylsulfide tetracarboxylic dianhydride; 3,3 ', 4,4 '-diphenyl sulfoxide tetracarboxylic dianhydride; 4,4 '-oxydiphthalic acid dianhydride; 3,4 '-oxydiphthalic acid dianhydride; 3,3 '-oxydiphthalic acid dianhydride; 3,3 '-benzophenone tetracarboxylic dianhydride; 4,4 '-carbonyl two O-phthalic acid dianhydride; 3,3 ', 4,4 '-diphenyl methane tetracarboxylic dianhydride; Two (4-(3, the 3-dicarboxyphenyi) propane dianhydride of 2,2-; Two (4-(3, the 3-dicarboxyphenyi) hexafluoropropane dianhydride of 2,2-; (3,3 ', 4,4 '-diphenyl) Phenylphosphine tetracarboxylic dianhydride; (3,3 ', 4,4 '-diphenyl) phenylphosphine oxide tetracarboxylic dianhydride; 2,2 '-two chloro-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride; 2,2 '-dimethyl-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride; 2,2 '-dicyano-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride; 2,2 '-two bromo-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride; 2,2 '-two iodo-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride; 2,2 '-two trifluoromethyl-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride; 2,2 '-bis-(1-methyl 4-phenyl)-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride; 2,2 '-bis-(1-trifluoromethyl-2-phenyl)-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride; 2,2 '-bis-(1-trifluoromethyl-3-phenyl)-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride; 2,2 '-bis-(1-trifluoromethyl-4-phenyl)-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride; 2,2 '-bis-(1-phenyl-4-phenyl)-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride; 4,4 '-bisphenol A dianhydride; 3,4 '-bisphenol A dianhydride; 3,3 '-bisphenol A dianhydride; 3,3 ', 4,4 '-diphenyl sulfoxide tetracarboxylic dianhydride; 4,4 '-carbonyl two O-phthalic acid dianhydride; 3,3 ', 4,4 '-diphenyl methane tetracarboxylic dianhydride; 2,2 '-bis-(1,3-trifluoromethyl-4-phenyl)-3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, and their all isomers, and the combination of above-mentioned substance.
For the manufacture of the halogen displacement polymerization of PEI and polyetherimide sulfone including, but not limited to, the reaction of two (phthalimide) of formula (8):
Wherein, R is as described above, and X is nitryl group or halogen.Such as, through type (9) corresponding acid anhydrides can form two-phthalimide (8) with the organic diamine condensation of formula (10):
Wherein, X is nitryl group or halogen,
H 2N-R-NH 2(10)，
Wherein, R is as described above.
The illustration of the amines of formula (10) comprises: ethylenediamine, propane diamine, trimethylene diamine, Diethylenetriamine, three second tetramines, hexamethylene diamine, heptamethylene diamines, eight methylene diamine, nine methylene diamine, decamethylene diamine, 1,12-dodecamethylene diamine, 1,18-octadecamethylene diamine, 3-methyl heptamethylene diamines, 4,4-dimethyl heptamethylene diamines, 4-methyl nine methylene diamine, 5-methyl nine methylene diamine, 2,5-dimethyl hexamethylene diamine, 2,5-dimethyl heptamethylene diamines, 2,2-dimethylated propyl diethylenetriamine, N-methyl-bis-(3-aminopropyl) amine, 3-methoxyl group hexamethylene diamine, 1,2-two (the amino propoxyl group of 3-) ethane, two (3-aminopropyl) thioether, Isosorbide-5-Nitrae-cyclohexane diamine, two-(4-aminocyclohexyl) methane, m-phenylene diamine (MPD), p-phenylenediamine (PPD), 2,4-diaminotoluene, 2,6-diaminotoluene, MXDP, terephthaldehyde's base diamines, 2-methyl-4,6-diethyl-1,3-phenylenediamine, 5-methyl-4,6-diethyl-1,3-phenylenediamine, benzidine, 3,3 '-dimethylbenzidine, 3,3 '-dimethoxy benzidine, 1,5-diaminonaphthalene, two (4-aminophenyl) methane, two (amino-3, the 5-diethyl phenyl of the chloro-4-of 2-) methane, two (4-aminophenyl) propane, two (b-amino-tert-butyl) toluene of 2,4-, two (p-b-amino-tert-butyl phenyl) ether, two (p-b-methyl-o-amino-phenyl-) benzene, two (p-b-methyl-o-Aminopentyl) benzene, 1,3-diaminourea-4-cumene, two (4-aminophenyl) ether and two (3-aminopropyl) tetramethyl disiloxane of 1,3-.The mixture of these amine can be used.Comprise sulfuryl group formula (10) amines illustration including but not limited to, diamino-diphenyl sulfone (DDS) and two (aminophenoxy phenyl) sulfone (BAPS).The combination of any one comprising above-mentioned amine can be used.
When existing or lack phase transfer catalyst, the Reactive Synthesis PEI of the alkali metal salt of the aromatic hydrocarbons that can be replaced with the dihydroxy of formula HO-V-OH by two (phthalimide) (8), wherein, V is as described above.The phase transfer catalyst be applicable at U.S. Patent number 5,229, open in 482.Particularly, the aromatic hydrocarbons that dihydroxy replaces can be used, bis-phenol, as bisphenol-A, or the combination of the alkali metal salt of the aromatic hydrocarbons of the alkali metal salt of bis-phenol and the replacement of other dihydroxy.
In one embodiment, the construction unit of PEI contained (5), wherein, each R is to phenylene or metaphenylene or the mixture comprising above-mentioned at least one independently; And T is the group of formula-O-Z-O-, wherein, two valence links of-O-Z-O-group are in 3,3 ' positions, and Z is 2,2-diphenylenepropane radical group (bisphenol-A group).And the construction unit of polyetherimide sulfone contained (6), wherein at least the R group of 50mole% has formula (4), and wherein Q is-SO 2-and remaining R group is to phenylene or metaphenylene or the combination comprising above-mentioned at least one independently; T is the group of formula-O-Z-O-, and wherein, two valence links of-O-Z-O-group are in 3,3 ' positions, and Z is 2,2-diphenylenepropane radical group.
Be manufactured in polymeric component described herein, individually or in combination with each other or PEI and polyetherimide sulfone can be being used together with polymeric material disclosed in other.In one embodiment, only PEI is used.In another embodiment, PEI: the weight ratio of polyetherimide sulfone can be 99:1 to 50:50.
PEI can have every mole 5000 to 100 measured by gel permeation chromatography (GPC), the weight average molecular weight (Mw) of 000 gram (g/ mole).In some embodiments, Mw can be 10,000 to 80,000.Molecular weight as used in this article refers to absolute weight average molecular (Mw).
As measured in metacresol at 25 DEG C, PEI can have the intrinsic viscosity being more than or equal to 0.2 deciliter/gram (dl/g).Within this scope, as measured in metacresol at 25 DEG C, intrinsic viscosity can be 0.35 to 1.0dl/g.
As used measured by the differential scanning calorimetry (DSC) of ASTM test D3418, PEI can have the glass transition temperature being greater than 180 DEG C, particularly, and 200 DEG C to 500 DEG C.In some embodiments, PEI, especially, PEI has the glass transition temperature of 240 to 350 DEG C.
As use 6.7 kilograms of (kg) weight, at 340 to 370 DEG C, by measured by American Society For Testing Materials (American Society for Testing Materials) (ASTM) DI 238, PEI can have the melt index (MI) of 0.1 to 10 Grams Per Minute (g/min).
Alternative halogen displacement polymerization for the manufacture of PEI (such as, having the PEI of structure (1)) is the method (in formula (8), X is chlorine) being called chlorine method of replacing.The following describes chlorine method of replacing: when there is the phenyl-phosphonite sodium catalyst of catalytic amount, 4-chloro-phthalic anhydride and m-phenylenediamine are reacted with the two chlorophthalimide producing m-phenylenediamine (CAS 148935-94-8).Subsequently when there is the catalyst be in o-dichlorohenzene or anisole solvent, two chlorophthalimide is by carrying out polymerisation with the chlorine replacement reaction of BPA disodium salt.Alternately, the mixture of the chloro-and 4-chloro-phthalic anhydride of 3-can be adopted to provide the mixture of isomeric pair of chlorophthalimide, and it can be polymerized by replacing with the chlorine of BPA disodium salt as described above.
Siloxane polyetherimide can comprise polysiloxanes/polyetherimide blocks copolymer, and based on the gross weight of block copolymer, it has and is greater than 0 and be less than the content of siloxane of 40 percetages by weight (wt%).The siloxane blocks of block copolymer contained (I):
Wherein, the R when occurring at every turn 1-6group independently selected from being made up of the following: have the replacement of 5 to 30 carbon atoms or unsubstituted, saturated, undersaturated, or aromatic monocyclic group, have the replacement of 5 to 30 carbon atoms or unsubstituted, saturated, undersaturated, or aromatic series polycyclic moiety, there is the replacement of 1 to 30 carbon atom or unsubstituted alkyl group, there is the replacement of 2 to 30 carbon atoms or unsubstituted alkenyl group, V is tetravalent linker, it is selected from the group be made up of the following: have the replacement of 5 to 50 carbon atoms or unsubstituted, saturated, undersaturated, or aromatic monocyclic and polycyclic moiety, there is 1 to 30 carbon atom replaces or unsubstituted alkyl group, there is 2 to 30 carbon atoms replace or unsubstituted alkenyl group, and comprise the combination of at least one in above-mentioned connector, g equals 1 to 30, and d is 2 to 20.The siloxane polyetherimide be purchased under trade name SILTEM* (trade mark of * SABICInnovative Plastics IP B.V.), can obtain from SABIC Innovative Plastics.
PEI can have the weight average molecular weight (Mw) in the scope with lower limit and/or the upper limit.Scope can comprise or not comprise lower limit and/or the upper limit.Lower limit and/or the upper limit can be selected from 5000, 6000, 7000, 8000, 9000, 10000, 11000, 12000, 13000, 14000, 15000, 16000, 17000, 18000, 19000, 20000, 21000, 22000, 23000, 24000, 25000, 26000, 27000, 28000, 29000, 30000, 31000, 32000, 33000, 34000, 35000, 36000, 37000, 38000, 39000, 40000, 41000, 42000, 43000, 44000, 45000, 46000, 47000, 48000, 49000, 50000, 51000, 52000, 53000, 54000, 55000, 56000, 57000, 58000, 59000, 60000, 61000, 62000, 63000, 64000, 65000, 66000, 67000, 68000, 69000, 70000, 71000, 72000, 73000, 74000, 75000, 76000, 77000, 78000, 79000, 80000, 81000, 82000, 83000, 84000, 85000, 86000, 87000, 88000, 89000, 90000, 91000, 92000, 93000, 94000, 95000, 96000, 97000, 98000, 99000, 100000, 101000, 102000, 103000, 104000, 105000, 106000, 107000, 108000, 109000, with 110000 dalton.Such as, PEI can have 5,000 to 10,000 dalton, 5,000 to 80,000 dalton, or 5000 to 70,000 daltonian weight average molecular weight (Mw).The PEI of main alkylamine modification will have compared with the lower molecular weight of the unmodified PEI begun and higher melt flows.
PEI can be selected from and form in group by the following: and PEI (such as at United States Patent (USP) 3,875,116; 6,919,422 and 6,355, described in 723); Silicone polyetherimide (such as at United States Patent (USP) 4,690,997 and 4,808, described in 686); Polyetherimide sulfone (as at United States Patent (USP) 7,041, described in 773), and their combination, each entirety of these patents is incorporated into this.
PEI can have the glass transition temperature in the scope with lower limit and/or the upper limit.Scope can comprise or not comprise lower limit and/or the upper limit.Lower limit and/or the upper limit, can be selected from 100,110,120,130,140,150,160,170,180,190,200,210,220,230,240,250,260,270,280,290,300, and 310 degrees Celsius.Such as, PEI can have the glass transition temperature (Tg) being greater than about 200 degrees Celsius.
PEI can substantially containing benzylic proton (benzylic proton) (being less than 100ppm).PEI can not contain benzylic proton.PEI can have the benzylic proton of the amount lower than 100ppm.In one embodiment, the amount of benzylic proton is between being greater than 0 between lower than 100ppm.In another embodiment, the amount of benzylic proton cannot detect.
PEI can be substantially free of halogen atom (being less than 100ppm).PEI can not halogen atom-containing.PEI can have the halogen atom of the amount lower than 100ppm.In one embodiment, the amount of halogen atom is between being greater than 0 between lower than 100ppm.In another embodiment, the amount of halogen atom cannot detect.
In one embodiment, PEI comprises PEI thermoplastic compounds, comprise: (a) PEI, b stabilizing agent that () is phosphorous, the Melt Stability increasing PEI is effectively measured, wherein, the stabilizing agent comprising phosphorus shows lower volatility and makes, measured by the thermogravimetry of the initial amount of the sample of the stabilizing agent by comprising phosphorus, under an inert atmosphere, with the rate of heat addition of 20 DEG C per minute, sample is heated to after 300 DEG C from room temperature, the sample being more than or equal to the initial amount of percent 10 by weight does not still evaporate.In one embodiment, phosphorous stabilizing agent has formula P-Ra, and wherein, R ' is H, alkyl, alkoxyl, aryl, aryloxy group or oxygen substituting group independently, and a is 3 or 4.The example of the stable PEI be applicable to like this can at U.S. Patent number 6, and 001, find in 957, it is incorporated into this as a whole.
The method can be included in when not extracting spinning fibre out in the step advancing or feed roller is collected spinning fibre.In the typical art methods described in as Fig. 4, when a series of extraction godet roller (be referred to as 409) (usually with high speed operation) extracts fiber to reduce their DENIER time, assemble guide plate (convergence guide) 406 and collect spinning fibre and on fiber, apply pulling force (pull).The fiber 407 that oil supply materials application extremely can be solidified by oiling device (finishapplicator) with the form of kiss roll (kiss roll) 408.In a device in accordance with the invention, the use of oil supply and kiss roll 408 is optional, and a series of extraction godet roller 409, can exempt completely in some embodiments.Therefore, according to the spinning head that the inventive system comprises according to Fig. 2 or 3, for collecting propelling or the feed roller (forwarding or feeding roll) of spinning fibre and collecting at least one bobbin (spool) or the winding reel (bobbin) that the meticulous DENIER being used for using further does not extract fiber out thereon.The method can comprise the step from melt spinning polymer production cured fiber.When the embodiment of the method can be included in and not make cured fiber experience extract step out, bobbin is collected the step of cured fiber.The embodiment of the method when not having air blast cooling cooling step, can produce cured fiber.When the method can be included in without any quenching (annealing, quenching) step, bobbin is collected the step of fiber.The method can be included in after spinning fibre leaves spinning head, the step of heating spinning fibre.
Cured fiber can have the dpf in the scope with lower limit and/or the upper limit.Scope can comprise or not comprise lower limit and/or the upper limit.Lower limit and/or the upper limit can be selected from 0,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1,1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2,2.1,2.2,2.3,2.4,2.5,2.6,2.7,2.8,2.9,3,3.1,3.2,3.3,3.4,3.5,3.6,3.7,3.8,3.9,4,4.1,4.2,4.3,4.4,4.5,4.6,4.7,4.8,4.9 and 5dpf.Such as, according to some preferred embodiment, cured fiber can have the dpf be greater than in the scope of 0 to 2.5dpf.
Cured fiber can have the shrinkage factor in the scope with lower limit and/or the upper limit.Scope can comprise or not comprise lower limit and/or the upper limit.Lower limit and/or the upper limit can be selected from 0,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1,1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2,2.1,2.2,2.3,2.4,2.5,2.6,2.7,2.8,2.9,3,3.1,3.2,3.3,3.4,3.5,3.6,3.7,3.8,3.9,4,4.1,4.2,4.3,4.4,4.5,4.6,4.7,4.8,4.9 and 5%.Such as, according to some preferred embodiment, cured fiber can have the shrinkage factor being less than or equal to 2%.
Embodiment also relates to a new nozzle design, and these designs are applicable to using high viscosity amorphous engineering thermoplasties to manufacture the fiber with low denier and low-shrinkage.Condition of high voltage is used (such as with needs, 1500 to 2000psi) different with the known processing maintaining the equally distributed polyether-imide fiber of the melt crossing spinneret hole, the spinning head of the various embodiment of design consideration can be low to moderate 400psi (such as, in 400 to 1500psi scope, preferably, in 400 to 1200psi scope, most preferably, within the scope of 400-1000psi) pressure under be uniformly distributed.Die design and corresponding spinning head allow amorphous thermoplastic, as PEI melt spinning becomes meticulous denier fiber.These embodiments can in whole die head the melt canal of wholecircle shape, dead space is reduced to minimum, or suspend (hang up) amorphous material and will collect or eddy current and not runny region, and suspend (hang up) and degrade, discharging the material of degraded subsequently off and on in melt stream stock.The L/D ratio rate of melt canal can be optimize for amorphous material, and distribution channel can be designed to reduce the shearing on material, and the more high viscosity of the amorphous material of use melt state is to obtain crossing being uniformly distributed of spinning head melt.Be designed in advised things by similar, no matter how DENIER previously can not be spun into the material of fiber at all, can spinning and being wrapped on bobbin, and optimized the method to realize finer denier fibers.
Concrete embodiment relates to spinning head and/or comprises a filament spinning component for spinning head, and it is for the unpumped polyether-imide fiber of amorphous by the composition production comprising amorphous PEI 2.5dpf at the most.Spinning head does not need to have distribution grid.
Spinning head can comprise the die head with multiple circular melt canals, and wherein, each circular melt canal has length and diameter.The length of each circular melt canal: the ratio of diameter can be 1:1,2:1,3:1,4:1,5:1,6:1,7:1,8:1,9:1,10:1,11:1, or 12:1.Such as, according to some preferred embodiment, the length of each circular melt canal: the ratio of diameter can be 2:1 to 6:1.
According to a kind of embodiment, compared with the identical spinning head comprising distribution grid, this spinning head can operate under a reduced pressure.According to various embodiment, do not have the operating pressure of the spinning head of distribution grid relative to the identical spinning head comprising distribution grid, can decline certain percentage.This percentage can in the scope with lower limit and/or the upper limit.Scope can comprise or not comprise lower limit and/or the upper limit.Lower limit and/or the upper limit can be selected from 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43,44,45,46,47,48,49,50,51,52,53,54,55,56,57,58,59 and 60%.Such as, according to some preferred embodiment, according to various embodiment, there is no the operating pressure of the spinning head of distribution grid relative to the identical spinning head comprising distribution grid, the percentage of at least 40% can be reduced.
Spinning head may further include at least one screen modules filter (screen pack filter) be combined with die head, so that composition is distributed to die head.Screen modules filter can have the screen size (screen size) in the scope with lower limit and/or the upper limit.Scope can comprise or not comprise lower limit and/or the upper limit.Lower limit and/or the upper limit can be selected from 100,110,120,130,140,150,160,170,180,190,200,210,220,230,240,250,260,270,280,290,300,310,320,330,340,350,360,370,380,390,400,410,420,430,440,450,460,470,480,490 and 500 orders.Such as, according to some preferred embodiment, screen modules filter can have 200 to 400 object US screen sizes.
Other embodiment relates to amorphous polymer fiber.Fiber can be extracted out, but even if in unpumped state, fiber can have excellent performance.
According to various embodiment, unpumped amorphous polymer fiber can have the DENIER in the scope with lower limit and/or the upper limit.Scope can comprise or not comprise lower limit and/or the upper limit.Lower limit and/or the upper limit, can be selected from 0,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1,1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2,2.1,2.2,2.3,2.4,2.5,2.6,2.7,2.8,2.9, and 3.Such as, according to some preferred embodiment, unpumped amorphous polymer fiber can have the DENIER being less than 2.5.
According to various embodiment, unpumped amorphous polymer fiber can have the shrinkage factor in the scope with lower limit and/or the upper limit.Scope can comprise or not comprise lower limit and/or the upper limit.Lower limit and/or the upper limit can be selected from 0,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1,1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2,2.1,2.2,2.3,2.4,2.5,2.6,2.7,2.8,2.9,3,3.1,3.2,3.3,3.4,3.5,3.6,3.7,3.8,3.9 and 4%.Such as, according to some preferred embodiment, unpumped amorphous polymer fiber can have and is greater than 0 to the shrinkage factor being less than or equal to 2%.
According to various embodiment, unpumped amorphous polymer fiber can have the polydispersity (Mw/Mn) in the scope with lower limit and/or the upper limit.Scope can comprise or not comprise lower limit and/or the upper limit.Lower limit and/or the upper limit, can be selected from 1,1.25,1.5,1.75,2,2.25,2.5,2.75,3,3.25,3.5,3.75,4,4.25,4.5,4.75,5,10,15,20,25,30,35,40,45,50, and 100.Such as, according to some preferred embodiment, according to various embodiment, unpumped amorphous polymer fiber can have the polydispersity (Mw/Mn) being more than or equal to 2.5.
According to various embodiment, unpumped amorphous polymer fiber can have the DENIER in the scope with lower limit and/or the upper limit.Scope can comprise or not comprise lower limit and/or the upper limit.Lower limit and/or the upper limit can be selected from 0,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1,1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2,2.1,2.2,2.3,2.4,2.5,2.6,2.7,2.8,2.9,3,3.1,3.2,3.3,3.4,3.5,3.6,3.7,3.8,3.9 and 4.Such as, according to some preferred embodiment, according to various embodiment, unpumped amorphous polymer fiber can have the DENIER being less than 2.2.
According to various embodiment, unpumped amorphous polymer fiber can have the intensity in the scope with lower limit and/or the upper limit.Scope can comprise or not comprise lower limit and/or the upper limit.Lower limit and/or the upper limit, can be selected from 1,1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2,2.1,2.2,2.3,2.4,2.5,2.6,2.7,2.8,2.9,3,3.1,3.2,3.3,3.4,3.5,3.6,3.7,3.8,3.9,4,4.1,4.2,4.3,4.4,4.5,4.6,4.7,4.8,4.9,5,10,15,20,25,30,35,40,45 and 50cN/dtex.Such as, according to some preferred embodiment, according to various embodiment, unpumped amorphous polymer fiber can have the intensity of at least 2.6cN/dtex.
According to various embodiment, unpumped amorphous polymer fiber can have the performance confirmed above, is also non-quenching (unanneled is unannealed) simultaneously.
Other embodiment relates to the article comprising unpumped amorphous polyether-imide fiber.Article can including but not limited to (comprising namely by polyether-imide fiber, one or more unannealed amorphous polyether-imide fibers, be wound around alternatively, braiding, knitting, spinning, or be additionally combined with dissimilar fiber) yarn made, the fabric be made up of unpumped amorphous fiber and/or yarn, and to comprise or based on the compound of the fabric be made up of unpumped amorphous fiber.The example of the compound be applicable to is including, but not limited to paper, such as, electrical paper (electrical paper), honeycomb paper, spin speciality paper (woven specialty paper), nonwoven speciality paper (non-wovenspecialty paper); Structural composites; Half structure compound.
In a word, the method comprised for the manufacture of unpumped amorphous polymer fiber comprises, under the pressure (such as, from 400 to 1000psi) of 400 to 1500psi, by spinning head melt extrusion to produce spinning fibre, wherein, melt comprises amorphous polymer composition, such as, PEI, can appoint ground, wherein, amorphous polymer composition can have the melt flow of 4 to 18g/10min; When not extracting spinning fibre out, spinning fibre collected by feed roller, produce cured fiber from spinning fibre, wherein, cured fiber has the dpf being greater than 0 to 2.5dpf, and cured fiber has the shrinkage factor being less than or equal to 2%; And when not making cured fiber experience extract step out, cured fiber is wound on bobbin.In any above-mentioned embodiment, one or more following conditions can be applied: the method can comprise further alternatively, when there is no annealing steps by fiber collecting on bobbin; The method may further include, and after spinning fibre leaves spinning head, heating spinning fibre, when not having air blast cooling cooling step, produces cured fiber; Melt comprises one or more crystalline material (crystalline material).
Amorphous polymer fiber, the fiber such as manufactured by said method, has and is less than 2.5, is less than 2.2, or is less than the DENIER of 2.0, and is greater than 0 to the shrinkage factor being less than or equal to 2%; Fiber can be polyether-imide fiber further, and such as, polyimide has the melt flow of 4 to 18g/10min alternatively, further alternatively, wherein, fiber has and is more than or equal to 2.5 polydispersity (Mw/Mn), and the intensity of at least 2.6cN/dtex alternatively.Fiber can be unannealed.The article comprising above-mentioned fiber comprise yarn, fabric and compound.
Not there is distribution grid for the production of useful spinning head in the said method of the unpumped polyether-imide fiber of amorphous (such as, there is 4 to 18g/10min melt flow) of 2.5dpf at the most; And there is the die head of multiple circular melt canal, wherein, each circular melt canal has length and diameter, and wherein, the length of each circular melt canal: the ratio of diameter is 2:1 to 6:1, alternatively, wherein, spinning head than comprise distribution grid identical spinning head operating pressure at least low 40% pressure under run, further alternatively, wherein, spinning head comprises at least one screen modules filter that is combined with die head further so that composition is distributed to die head, such as, have the filter of 200 to 400 object US screen sizes.
In following exemplary embodiment, further describe the present invention, wherein, all numbers and percentage are by weight, except as otherwise noted.
Embodiment
The material adopted in an embodiment listed by table 1.
Adopt two kinds of nozzle design in an embodiment.First, α nozzle design (AlphaSpinneret Design) (see Fig. 1) is adopted.Now by the nozzle design of these types of more detailed description.Secondly, the β assembly nozzle design (Beta PackSpinneret Design) (see Fig. 2 and 3) according to various embodiment of the present invention is adopted.
1. the description of α nozzle design
As shown in Figure 1, according to prior art, filament spinning component (spin pack) 100 comprises capillary spinneret plate 102, and it is assembled to the rectangular block in the heater jacket region of extruder, has about 0.25 inch gaps around it.Prior art filament spinning component 100, between base plate 101 and capillary spinneret plate 102, needs to install a series of distribution grid 103.Design distribution grid 103 is for providing pressure block (pressure block) melt to be evenly distributed to the rectangular array of 144 capillaries for both.Depend on the extruder of employing, these plates can be different size and shape.
Distribution grid 103 is very thin, only has the thickness of about 0.02 inch, and the melt canal of this material is only 0.01 inch diameter and 3/16 inchage.Melt canal restrictive is of a size of amorphous material and higher intraware pressure (interal pack pressure) creates strict flox condition.Intraware pressure causes the process window of limited material.It also causes separating out (plate out) at production period material or building up on the face of capillary spinneret plate 102.As time goes on this residue constantly accumulates and has to scrape off from face.This causes undesirable interruption in this process.
The Convective Heating that the temperature of filament spinning component 100 controls by installing assembly ambient air clearance space in an extruder realizes.The system of filament spinning component 100 is adopted more slowly to respond the change of service condition, such as temperature and pressure.In addition, usually observe the significant temperature loss from set point to filament spinning component, need operating personnel set point temperatures to be adjusted to higher than desired temperature about 20 degrees Celsius.
2. the description (" β component Design ") of new nozzle design
According to various embodiment, can be similar to shower head design for the capillary spinneret being produced melt-spinning fiber by PEI, because around circular components face, capillary spinneret can have equally distributed capillary array.
According to various embodiment, Fig. 2 illustrates the schematic diagram with the filament spinning component 200 of capillary spinneret 201.The special capillary spinneret 201 illustrated in fig. 2 has 72 capillaries 202, but can adopt the capillary of any applicable quantity.Capillary spinneret 201 can be arranged by interlayer together with distribution block 203 between base plate 204 and end cap 205.Distribution block 203 can have the multiple distribution holes 206 for melted material being distributed to capillary spinneret 201.End cap 205 can have the multiple through holes 207 that can aim in the hole 208 corresponding on base plate 204 with via bolt or other fastener fastening and compress filament spinning component 200.
According to various embodiment, Fig. 3 illustrates the schematic diagram with the filament spinning component 300 of capillary spinneret 301.The special capillary spinneret 301 illustrated in figure 3 has 144 capillaries 315, but can adopt the capillary 315 of any applicable quantity.Between end cap 305 and one or more base plates, capillary spinneret 301 can be arranged together with screen modules filter (screen pack filter) 302, first packing ring (gasket) 303 interlayer together with the second packing ring 304.As shown in Figure 3, the first base plate 306 and the second base plate 307 can be adopted.
End cap 305 can have the multiple through holes 308 that can aim in the hole 309 corresponding on the first base plate 306 with via bolt or other fastener, fixing and compress the parts of multiple filament spinning component 200.First base plate 306 can be fastened to the second base plate 307 (this bolt or other fastener through hole 310 be inserted through on the first base plate 306 enters the receiver hole 311 on the second base plate 307) via bolt or other fastener.
Second base plate 307 can comprise injection port 312, melted material can be injected into filament spinning component 300 by it, such as, from the extruder (this bolt or other fastener are inserted through the fastener hole 313 on the second base plate 307) via bolt or other fastener filament spinning component 300 is fastened to it.First base plate 306 can comprise one or more distribution mouth 314 and continue to flow through filament spinning component 300 to allow melted material.
Embodiment described below adopts filament spinning component 300 as shown in Figure 3, because the capillary spinneret 301 with 144 capillaries causes the throughput similar with old " α " component Design.
In this design, melt is delivered to assembly face and has been simplified and has improved (streamline, pipelining).Eliminate distribution grid, and complete the distribution of melt only by net-filter assembly filter 302.Distribution mouth 314 provides the active wheel system of wholecircle shape (full round runner system) melt stream to be introduced into the center of screen modules filter dorsal part from machine exit.Packing ring 303 and 304 can after filter 302 (that is, on the side closest to the first base plate 306) provide enough cavitys, to allow the equal uniform flow forming material after silk screen.Once form enough pressure after screen modules filter, melt passes and enters in spinning head.Then as shown in Figure 4, via the pressure formed, it is extruded by capillary 315, and it be drawn on take up roll (take uproll) and be wound on one or more winding reel (bobbin) 410.
Fig. 4 is the schematic diagram of fiber process 400.Melt stream 401 from extruder can be fed to measuring pump 402, by filter 403, and by spinning head 404.After leaving spinning head 404, melt stream 401 can be made through air anneal 405.Converge guiding piece (convergenceguide) 406 and fiber 407 can be guided to feeding means (finish applicator) 408, and be wound on one or more winding reel 410 by a series of extraction godet roller (drawing godet) 409.
The various spinning head of design and structure is to allow research length different in capilar bore and diameter (L/D) ratio (1 to 6), and the diameter of 0.2mm to 1.0mm.In addition, depend on viscosity of material, use screen size scope to be 200 to 400 object screen modules filters.
In Hills GHP bi-component melt spinning extrusion line, this spin pack design is installed.Design it to be assemblied in the identical package shell (pack envelope) of α design use.The new design of configuration is to provide enough spaces at assembly head thus to allow to control with the direct Contact Temperature in the heating tape (highwattage heater band) of high wattage.New design provides more closely and thermal control faster in filament spinning component face (key component in melt spinning process).
The description of PEI is manufactured by new β nozzle design
Under 300 degrees Fahrenheit, drying material will cause any moisture of depolymerization to remove in 4 to 8 hours under melt state.
Assembling and placement filament spinning component in preheating oven, to make it reach operating temperature before being mounted in machine and melt stream.
Before any material is introduced into extruder, open machine and preheating several hours.Once reach temperature, the funnel above extruder utilizes automatic loading device, in extruder, load spherolite.Open Melt Pump, then open extruder.These are Non-follow control until two melt stream stocks all from machine out, and realize rational melt pressure and speed.Subsequently, at the whole remainder of process, by pressure automatic control melt pressure.
When temperature and pressure arrives the balance of wishing, stop pump and extruder, and shift out spinning head from baking oven and be mounted to machine.Outside heating tape controls thermocouple together with it and is mounted on filament spinning component.Open this unit subsequently and be set to the set point of hope.
Subsequently, Melt Pump and extruder is reopened.In pail for used dressings, collect the fiber extruded, and cultivate spinning head and reach operating temperature.When this happens, get melt sample and make fiber, to determine melt proportion.
Once temperature and pressure becomes level, subsequently by tensile fiber in thread suction gun, and the charging or advance on roller of (spin finish kiss roll) is collected under optional spinning oil-feeding kiss roll.The speed of pump and propelling roller limits the diameter of the fiber obtained, or the DENIER (dpf) of every filament.Once obtain the dpf wished, load fiber subsequently in wrapping head.Fibre bundle is wound up at least one bobbin or multiple winding reel and is used for using subsequently in downstream process by wrapping head.
For the PEI fiber of 2dpf and more low denier, we are with 4 to 6rpm process pump, and run with 1500m/min to 2500m/min and advance roller.Do not need further stretching at any reel off raw silk from cocoons (draw roll) on roller, or annealing with any relax rolls (relaxing roll) of this process configuration does not need.
The description of PEI is manufactured by old α nozzle design
The step of α nozzle design is identical in the process steps started and operate.When you want the fiber realizing 2dpf or meticulousr, there is difference.Be necessary in this case reeling off raw silk from cocoons drawing of fiber on roller and attempt to control the shrinkage factor in relax rolls (relax roll).
For using the 2dpf PEI fiber of this set, we operate Melt Pump between 5 to 7rpm, and feed roller is 1500m/min to 2500m/min.The feed roller operated between 1500m/min to 2500m/min is maintained, the relax rolls maintaining the extraction roller (draw roll) between 2250m/min to 3000m/min and also maintain at the temperature of 200 degrees Celsius between 2250m/min to 3000m/min at the temperature of 200 degrees Celsius at the temperature of 200 degrees Celsius.By being increased in the annealing that the upper temperature being wound around quantity and godet roller of godet roller (godet) can control fiber and the shrinkage factor obtained.
For measuring the technology of fiber denier
DENIER or the line density of fiber is measured according to ASTM D1907-07 test method.For the rotation of specified quantity, the spool of girth one meter is wound around fiber, then weighs.The quality of sample and length determine line density or the DENIER of each fiber filaments.
For measuring the technology of fibre shrinkage
Fibre shrinkage test is implemented according to ASTM D2559 dry heat method.The fiber sample of long 1 meter is put into baking oven and is exposed to the time of applicable constant temperature scheduled volume.Shift out sample from baking oven subsequently, measure length subsequently.Itself and initial 1 meter of length depart from the percentage determining that it changes or shrinks.
Embodiment 1
The object of this embodiment manufactures PEI fiber according to our invention.Except adopting 1 1/4 inch extruder and β component Design, manufacture fiber according to above-described step.Use the 0.6mm capillary spinneret with 4L/D, and use 325 order screen modules filters.
The fiber produced has the dpf of 2 and is less than the shrinkage factor of 2%.Unexpectedly, after initial reception, when not needing to stretch or anneal fiber, time directly from spinnerette, fiber demonstrates the combination of low denier and low-shrinkage.When not destroying, manufacturing fiber with the speed of 1500m/min to 2250m/min and continuing within least 2 hours, to be possible.This embodiment advantageously proves, can make low denier fiber by the PEI of the molecular weight distribution with at least 2.5.
Embodiment 2
The object of this embodiment is the execution of the method for repetition embodiment 1, and various embodiment according to the present invention manufactures polyether-imide fiber.Fiber is manufactured according to above-described step.0.6mm capillary spinneret uses together with 325 order screen modules filters with 4L/D.The fiber obtained has 1.8dpf and is less than the shrinkage factor of 2%.
When not needing to stretch (extraction) or annealing fiber, when directly producing from spinning head under low shear conditions, the fiber obtained demonstrates the combination of low denier and low-shrinkage.When not destroying, manufacturing fiber with the speed of 1500m/min to 2250m/min and continuing within least 2 hours, to be possible.This embodiment advantageously proves, can make low denier fiber by the PEI of the molecular weight distribution with at least 2.5.
Embodiment 3
The object of this embodiment is when comprising lower object screen modules filter, manufactures polyether-imide fiber according to the embodiment of the present invention.Except using 200US order number screen modules filter (200US mesh screen pack filter), the process according to embodiment 1 and embodiment 2 manufactures fiber.
When not needing to stretch or anneal fiber, under low shear conditions, when directly producing from spinning head, the fiber obtained demonstrates the combination of low denier and low-shrinkage.It is possible for manufacturing the 2dpf fiber with 1.9% shrinkage factor.When not destroying, manufacturing these fibers with the speed of 1500m/min to 2250m/min and continuing at least 2 hours.This embodiment advantageously proves, can make low denier fiber by the PEI of the molecular weight distribution with at least 2.5.
Embodiment 4
The object of this embodiment is when comprising the screen modules filter of more low mesh number, manufactures polyether-imide fiber according to the embodiment of the present invention.Except using 400 order screen modules filters, the process according to embodiment 1 and embodiment 2 manufactures fiber.
When not needing to stretch or anneal fiber, under low shear conditions, when directly producing from spinning head, the fiber obtained demonstrates the combination of low denier and low-shrinkage.It is possible for manufacturing the 2dpf fiber with 1.8% shrinkage factor.When not destroying, manufacturing these fibers with the speed of 1500m/min to 2250m/min and continuing at least 2 hours.This embodiment advantageously proves, can make low denier fiber by the PEI of the molecular weight distribution with at least 2.5.
Embodiment 5
The object of this embodiment manufactures polyether-imide fiber according to the embodiment of the present invention.Except using 2L/D spinning head, manufacture fiber according to the process described in example 4.
When not needing to stretch or anneal fiber, when directly producing from spinning head, the fiber obtained demonstrates the combination of low denier and low-shrinkage.It is possible that manufacture has the 2dpf fiber being less than 2% shrinkage factor.When not destroying, manufacturing these fibers with the speed of 1500m/min to 2250m/min and continuing at least 2 hours.This embodiment advantageously proves, can make low denier fiber by the PEI of the molecular weight distribution with at least 2.5.
Embodiment 6
The object of this embodiment is the execution of repetition embodiment 5 and manufactures PEI fiber according to the embodiment of the present invention.
When not needing to stretch or anneal fiber, under low shear conditions, when directly producing from spinning head, the fiber obtained demonstrates the combination of low denier and low-shrinkage.It is possible that manufacture has the 2dpf fiber being less than 2% shrinkage factor.When not destroying, manufacturing these fibers with the speed of 1500m/min to 2250m/min and continuing at least 2 hours.This embodiment advantageously proves, can make low denier fiber by the PEI of the molecular weight distribution with at least 2.5.
Embodiment 7
The object of this embodiment manufactures polyether-imide fiber according to the embodiment of the present invention.Except running except the present embodiment on 1 inch screw with β component Design, manufacture fiber according to above-described process.This set uses 0.2mm capillary and the 200 order screen modules filters with 4L/D.
When not needing to stretch or anneal fiber, under low shear conditions, when directly producing from spinning head, the fiber obtained demonstrates the combination of low denier and low-shrinkage.It is possible for manufacturing the 1.7dpf fiber with 1.1% shrinkage factor.When not destroying, manufacturing these fibers with the speed of 1500m/min to 2250m/min and continuing at least 2 hours.For this embodiment, less capillary size causes component pressure to rise to 1400psi.This embodiment advantageously proves, can make low denier fiber by the PEI of the molecular weight distribution with at least 2.5.
Embodiment 8
The object of this embodiment manufactures polyether-imide fiber according to the embodiment of the present invention.Except using β component Design to run except the present embodiment on 1 inch extruder, manufacture fiber according to above-described process.Spinning head is the 0.4mm capillary diameter with 4L/D ratio.Same in this scheme, adopt 200 order screen modules filters.
When not needing to stretch or anneal fiber, under low shear conditions, when directly producing from spinning head, the fiber obtained demonstrates the combination of low denier and low-shrinkage.It is possible for manufacturing the 2dpf fiber with 1.5% shrinkage factor.When not destroying, manufacturing these fibers with the speed of 1500m/min to 2250m/min and continuing at least 2 hours.This embodiment advantageously proves, can make low denier fiber by the PEI of the molecular weight distribution with at least 2.5.
Embodiment 9 (comparative example)
The object of this embodiment manufactures polyether-imide fiber according to prior art " α " spin pack design (as shown in Figure 1, it comprises distribution grid).Manufacture fiber according to process above and obtain following result.Use 9011 manufacture PEI fiber.The extruder of 1 inch runs the present embodiment.Use 0.6mm capillary spinneret and the 325 order screen modules filters with 4L/D.
Result shows, when under high shear conditions., such as, under pressure is more than or equal to the condition of 1400psi, when manufacturing PEI fiber, the unpumped and unannealed PEI fiber manufacturing the low-shrinkage shown according to the fiber of various embodiment production according to the present invention is impossible.More particularly, in the present embodiment, producd fibers under the shrinkage factor of 2.2dpf and 4%.In addition, in order to use α filament spinning component to obtain fiber, being necessary to extract fiber out, subsequently their being annealed to attempt to realize 2dpf.This method causes shrinkage factor higher than the method for various embodiment according to the present invention subsequently.In addition, compared with the pressure (400 to 600psi) of the embodiment before major part, this example adopts the high component pressure more than 1500psi.
Table 2 is provided in the summary of the result obtained in embodiment 1-9.
Although described in detail the present invention with reference to some preferred form of the present invention, other form has been possible.Therefore, the spirit and scope of claim of enclosing, should not be confined to the description of the preferred form comprised in this article.
The all paper simultaneously submitted to this description and the content of document and for public examination those disclosed, be combined in herein by reference.
Unless otherwise expressly stated, otherwise can be identical by having, the alternative feature of equivalent or similar object replaces all features disclosed in this description (comprising any claims, summary and accompanying drawing).Therefore, unless otherwise expressly stated, disclosed each feature is only the general equivalence of series or a kind of embodiment of similar characteristics.

Claims (18)

1. a method, comprising:
Under the pressure of 400 to 1500psi, pass through spinning head melt extrusion to produce spinning fibre, wherein, described melt comprises amorphous polymer composition;
On feed roller, described spinning fibre is collected when not extracting described spinning fibre out,
The fiber of solidification is produced by described spinning fibre,
Wherein, the fiber of described solidification has the dpf being greater than 0 to 2.5dpf,
Wherein, the fiber of described solidification has the shrinkage factor being less than or equal to 2%; And
When not making the fiber experience of described solidification extract step out, by the Filament-wound Machine of described solidification on bobbin.
2. method according to claim 1, wherein, described amorphous polymer composition has the melt flow of 4 to 18g/10min.
3. the method according to any one of claim 1 or 2, wherein, described pressure is 400 to 1000psi.
4. according to the method in any one of claims 1 to 3, be included in when there is no annealing steps further, by described fiber collecting to described bobbin.
5. method according to any one of claim 1 to 4, wherein, the fiber of described solidification is produced when not forcing Air flow step.
6. method according to any one of claim 1 to 5, wherein, described method is included in after described spinning fibre leaves described spinning head further, heats described spinning fibre.
7. method according to any one of claim 1 to 6, wherein, described melt comprises one or more crystalline material.
8. method according to any one of claim 1 to 7, wherein, amorphous polymer composition comprises PEI.
9. a unpumped amorphous polymer fiber, have be less than 2.5 DENIER and be greater than 0 to the shrinkage factor being less than or equal to 2%.
10. unpumped amorphous polymer fiber according to claim 9, wherein, described polymer fiber is polyether-imide fiber, and wherein, described fiber has the polydispersity (Mw/Mn) being more than or equal to 2.5.
11. unpumped amorphous polyether-imide fibers according to any one of claim 9 to 10, wherein, described fiber has the DENIER being less than 2.2.
12. unpumped amorphous polyether-imide fibers according to any one of claim 9 to 11, wherein, described fiber has the intensity of at least 2.6cN/dtex.
13. unpumped amorphous polyether-imide fibers according to any one of claim 9 to 12.
14. 1 kinds of article, comprise the unpumped amorphous polyether-imide fiber according to any one of claim 9 to 13.
15. 1 kinds of spinning heads, for the unpumped polyether-imide fiber of amorphous by the composition production comprising amorphous PEI 2.5dpf at the most, described spinning head comprises
There is no distribution grid; And
Have the die head of multiple circular melt canal, wherein, each circular melt canal has length and diameter, and wherein, each circular melt canal length: the ratio of diameter is 2:1 to 6:1.
16. spinning heads according to claim 15, wherein, described spinning head than comprise distribution grid identical spinning head operating pressure at least low 40% pressure under operate.
17. according to claim 15 to the spinning head according to any one of 16, and wherein, described spinning head comprises at least one screen modules filter be combined with described die head further, so that described composition is distributed to described die head.
18. spinning heads according to claim 17, wherein, described screen modules filter has 200 to 400 object US screen sizes.
CN201380037820.1A 2012-08-06 2013-07-31 Produce method, fine amorphous polymer fiber and the spinning head for producing this fiber of fine amorphous polymer fiber Expired - Fee Related CN104471119B (en)

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